Fogged, direct-positive silver halide photographic material containing a rhodium salt desensitizer and a bispyrazolone dye stabilizer

ABSTRACT

A direct - positive light - sensitive silver halide material containing fogged silver halide grains and a rhodium salt as a desensitizer to increase the reversal speed, which material comprises a bis-pyrazolone dye having an absorption maximum in the range from 590 to 690 mu, said bis-pyrazolone dye having a methine chain connecting two pyrazolone nuclei thereof, said methine chain consisting of 5 unsubstituted methine groups.

Diiited States Patent 1191 Furuya et a1.

[73] Assignees Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 221- Filed: Apr. 26, 1973 211 Appl. No.: 354,842

[30] Foreign Application Priority Data May 4, 1972' Japan .1 47-43679 [52] U.S. Cl 96/101, 96/107, 96/108,

, 96/109, 96/125, 96/139, 96/140 [51] Int. Cl. G03c 1/28, G03c 1/34, G03c 1/36 7 [58] Field of Search ..96/l07,108,109,101,

1 1 Feb. 18, 1975 [56] References Cited UNITED STATES PATENTS 2,717,833 9/1955 Wark 96/108 3,576,636 4/1971 Matsui et al. 96/101 3,656,961 4/1972 Hayakawa 6 31. 96/108 3,738,846 6/1973 Kamano 61 al 1. 96/101 Primary Examiner-Ronald H. Smith Assistant ExaminerWon H. Louie, Jr. Attorney, Agent, or FirmBierman & Bierman [57] ABSTRACT A direct positive light sensitive silver halide material containing fogged silver halide grains and a rho-- dium salt as a desensitizer to increase the reversal speed, which material comprises a bis-pyrazolone dye having an absorption maximum in the range from 590 to 690 mu, said bis-pyrazolone dye having a methine chain connecting two pyrazolone nuclei thereof, said methine chain consisting of 5 unsubstituted methine groups.

2 Claims, No Drawings This invention relates to a light-sensitive silver halide photographic material. More particularly, the invention pertains to a solarization type direct-positive lightsensitive material.

Generally, a direct-positive light-sensitive material utilizing Harschel effect (a so-called Harschel type direct-positive light-sensitive material) and a directpositive light-sensitive material utilizing solarization (a so-called solarization type direct-positive light-sensitive material) have been known as typical direct-positive light-sensitive materials.

It is well known that the solarization type directpositive light-sensitive material is of such a type that moderately pre-fogged nuclei effect subtraction due to excess exposure to give a direct-positive image, and hence is essentially different from the Harschel type direct-positive light-sensitive material which utilizes the phenomenon that pre-fogged nuclei effect subtraction due to red light or infrared light.

Ordinarily, the solarization type directpositive lightsensitive material has moderately been pre-fogged by application of light or by adoption of such chemical means as using a fogging agent, and it is well known that subtraction of the fog is promoted by use of a desensitize'r to increase the reveral speed of the lightsensitive material. It is also well known that when a rhodium salt is used as the desensitizer in the above case, there is obtained a solarization .type direct-positive light-sensitive material which is relatively high in speed.

Despite of its relatively high in speed, however, the solarization type direct-positive light-sensitive material containing a rhodium salt as the desensitizer is low in safeness to darkroom light and hence is inconvenient in handling. This tendency is particularly marked when the said light-sensitive material has been optically sensitized by incorporation of a sensitizing dye or the like and has been made higher in speed by interaction of said dye with the rhodium salt. Consequently, the lightsensitive material is deteriorated in safeness to a darkroom light of orange to red color, which is ordinarily used in a darkroom, with the result that the density is lowered.

A principal object of the present invention is to provide a solarization type direct-positive light-sensitive material which is not only high in speed but also has en-.

hanced safeness to darkroom light.

As the result of extensive studies, we have found that the above-mentioned object can successfully be accomplished by incorporating into at least one'of the photographic layers, e.g., protective layer, inter layer, emulsion layer, sub layer or backing layer, ofa solarization type direct-positive lightsensitive material containing a rhodium salt as a desensitizer, a certain dye in a proportion of 1 to 500 mg. per 100cm of the lightsensitive material.

The dye used in the present invention is required to have an absorption maximum in the range from 590 to 690 mu. In case a dye having an absorption maximum exceeding the said range has been used, the light-' sensitive material is insufficient in safeness to darkroom light, while in case a dye having an absorption maximum smaller than said range has been used, the light-sensitive material gives an image which is unsatisfactory in photographic property. The amount of the dye used in the present invention should be in the range from 1 to 500 mg. per 100 cm of the effective area of the light-sensitive material. If the amount of the dye is out of said range, either the photographic property or the safeness to darkroom light is unsatisfactory.

Typical examples of the dye used in the present invention are shown below, but dyes usable in the present 40 invention are not limited to these.

Absorption maximum 635 m Absorption maximum 612 nm.

Absorption maximum 620 m Absorption maximum 617 nm.

Absorption maximum 670 111p.

Produced by Nihon Kayaku 00.; absorption maximum 595 m Absorption maximum 630 my.

Absorption maximum 645 m 3 U rroo-o :-c1r=or1 orr=c cooon 4 v a i IIOOCC-CCCH=CIILCII=O-C--C0OJ[ n u A I u N on OII l-0ll CO0H coon H5020OCCCCH=CHCH=CCCOOC2115 )2 l N =on o=c\ (6)..; KayakuAlizarin Blue HRL 0 NHZ II I A SO;Na Naogs 0 NH -NHCOCH3 8) Il\laO;S

Q Q a)2-N(C2H5)2 ms )2 zHs)2 The dye used in the present'invention is preferably such that it is water-soluble and leaves no stains after development. The dye is dissolved in a proper solvent such as water, methanol, ethanol or acetone, and then incorporated into any of the photographic layers of a solarization type direct-positive light-sensitive material. In this case, the dye is preferably incorporated into the protective layer or the like layer which is upper than the light-sensitive layer. If necessary, however, the dye is incorporated into the backing layer, sub layer or the like layer which is lower than the light-sensitive layer. In case the dye has no influence on photographic properties of the light-sensitive material, it may be incorporated into the light-sensitive layer or into the inter layer or the like layer adjacent to the light-sensitive layer. The amount of the dye to be incorporated is l to 500 mg., preferably about 5 to mg., per 100 cm of the effective area of the light-sensitive material.

The solarization type direct-positive light-sensitive material according to the present invention which is prepared'in the above manner not only has excellent speed and safeness to darkroom light but also is excellent in other photographic properties.

The rhodium salt used in the present invention is a water-soluble rhodium salt suchas rhodium chloride or rhodium bromide which is used as a desensitizer. Generally, the rhodium salt is added at the time of emulsification or physical ripening of silver halide, and is ordinarily used in a proportion within the range from about 0.5 to 400 mg. per mole of silver halide. The silver halide may be any of such silver halides as silver chlorobromide, silver bromide, silver chloroiodobromide and silver iodobromide, and the silver halide emulsion may be prepared according to any of acid process, neutral process and ammonia process. In this case, gelatin is ordinarily used as the protective colloid. Alternatively,

however, other hydrophilic protective colloid such as albumin, polyvinyl alcohol and the like may be used either singly or in admixture with gelatin or in the form of a mixture of two or more.

The silver halide emulsion is fogged according to an ordinary procedure witha reducing agent such as stannous chloride, formaldehyde or thiourea dioxide, or with a salt of a metal high in potential than silver such as potassium chloroaurate, or with a combination of the two. Ordinarily, the reducing agent is used in a proportion of about-0.05 to 400 mg., and the salt ofa metal higher in potential than silver is used in'a proportion of about 0.5 to 100 mg., per mole of silver halide.

The light-sensitive material according to the present invention may contain various photographic additives, e.g., a hardener such as formaldehyde, glyoxal or such substituted fatty acid as mucobromic acid, an extender such as saponin, a stabilizer, couplers, etc. More pref- The thus prepared sample was allowed to stand with the emulsion sideup and at a distance of l m. under a 20W darkroom lamp with a red filter for such a period oftime as shown in Table l. Thereafter,the sample was subjected to ordinary development (using, for example, the D72 developer produced by Kodak Co.) and then measured in density to obtain the results as set forth in Table 1.

Table 1 Amount Reversal Density per speed Allowed Allowed Allowed Allowed Allowed Dye I em (relative to stand to stand to stand to stand to stand value) for for for for for 0 min. 3min. 5 min. l0 min. "0 min I00 2.68 2.65 2.60 2.55 2.4.l' Compound (I) 60 mg. 92 2.72 2.70 2.69 2.67 2.63 Compound (3) I50 mg. 90 2.63 2.63 2.6] 259 2.55 Compound (7) 120 mg. 95 2.65 2.65 2.64 2.62 2.60

erably, the light-sensitive material is optically sensitized with any of such spectral sensitizersas cyanine and mero'cyanine dyes. 3

The present invention is illustrated in further detail below with reference to examples, but the scope of the invention is not limited to the examples.

- EXAMPLE 1 I Liquid 1:

Gelatin g. Citric acid 0.4 g. Water 400 cc.

Liquid II: 7

Silver nitrate g 40 g; Water 400 cc.

Liquid lll:

Sodium chloride 1 14 g. Potassium bromide 12 g. Rhodium chloride solution* 8 cc. Water 90 cc.

Liquid .lV:

Gelatin v 70 g. Potassium iodide 0.2 g. Water 300 cc.

A solution ol'0.l g. of RhCI AHJ) in I00 cc. ol'a aqueous sodium chloride 20, From Table 1, it is understood that even when al- 25 was observed in reversal speed of the sample according to the present invention.

EXAMPLE 2 Liquid l: j

Gelatin l6 g. Water 110 cc.

Potassium bromide 34 g. Potassium iodide 0.7 g. Rhodium chloride solution l.5 cc. Liquid II: v Silver nitrate 48 g.

35 Water 400 .cc.

Ammonia water Equivalent The liquid [1 was added to the liquid 1 to prepare an emulsion. Theemulsion was ripened at C. for 10 minutes and then neutralized to a pH of 6.5 by addition solution. I 40 of acid. Subsequently, the emulsion was washed. with water, stirred at 50C. for l0 minutes together with [2 The liquid ll was added at 50C. to the liquid l, and g. of gelatin and then properly l'ogged with a mixture of then the liquid III was added to the resulting mixture a reducing-agent and a gold compound. One halfot' the with stirring to prepare an emulsion. The emulsion was thus treated emulsion was incorporated with a hard ripened at 50C. for 40 minutes and then charged with ener and a surface active agent to form an emulsion the liquid IV. After 10 minutes, the emulsion was 'ad- (A), and the other half of the emulsion was incorpousted to a pH of 8.8 by addition of alk and 5 cc. of rated with an ortho-sensitizing dye 3.,3'-9-triethyloxa 4 percent formaldehyde solution was added thereto. acarbocyanine iodide, a hardener and a surface active After fogging y incubation at C. for 15 m nutes, 50 agent. Each of the emulsions (A) and (B) was coated the emulsion was neutralized to a pH of 6.0 by addition on a transparent support. Subsequently, a protective of acid. Subsequently, the emulsion was incorporated layer-forming solution incorporated with each of such with an ortho-sensitizing dye 3,3-9-triethyloxacardyes as shown in Table 2 was coated on the resulting bocya riine iodide, each of such dye as shown in Table emulsion layer and then dried to prepare a sample. The l, a hardener and a surface active agent, coated on a thus prepared sample was treated in the same manner transparent support and then dried to prepare a samas in Example 1 and then measured in density to obtain pl the results as set forth in Table 2. t

Table 2 Amount Reversal Density per speed Allowed Allowed Allowed Allowed Allowed Emul- Dye 100 cm (relative to stand to stand to stand to stand to stand sion value) for for for for for 0 min. 3min. 5 min. l0'min. 20min.

A 1 20 4.07 4.02 3.95 3.88 3.56 A Compound (2) 25 mg; 19 4.08 4.08 4.07 4.06 4.05 B 100 4.01 3.75 339 3.03 2.05 B Compound (2) 25 mg. 96 4.02 4.0] 3.98 3.85 3.70 B Compound(6) 30mg. 95 4.00 4.00 3.95 3.83 3.65 B Compound (4) 35 mg. 93 3.99 3.95 3.89 3.80 3.71 B Compound(5) 50mg. 4.03 4.01 4.00 3.95 3.88 B 30 mg. 98 4.0l 4.00 3.98 3.90 3.95

Compound (8) From Table 2, it is understood that each sample according to the present invention is scarcely degraded in density even when allowed to stand under a darkroom light for a long period of time.

What we claim is: 1. A direct-positive light-sensitive silver halide material containing fogg ed silver halide grains and a rhodium salt as a desensitizer to increase the reversal speed, which material comprises a bis-pyrazolone dye having an absorption maximum in the range from 590 to 690 mp., which dye is present in an amount of l to 500 mg. per 100 cm of the effective area of said sensitive material, said bis-pyrazolone dye having a methine chain connecting two pyrazolone nuclei thereof, said methine chain consisting of 5 unsubstituted methine groups.

2. A direct-positive light-sensitive material according to claim 1, wherein said bis-pyrazolone dye is selected from the following compounds: 

1. A DIRECT-POSITIVE LIGHT-SENSITIVE SILVER HALIDE MATERIAL CONTAINING FOGGED SILVER HALIDE GRAMS AND A RHODUM SALT AS A DENSENSITIZER INCREASE THE REVERSAL SPEED, WHICH MATERIAL COMPRISES A BIS-PYRAZOLONE DYE HAVING AN ABSORPTION MAXIMUM IN THE RANGE FROM 590 TO 690 MU, WHICH DYE IS PRESENT IN AN AMOUNT OF 1 TO 500 MG. PER 100 CM2 OF THE EFFECTIVE AREA OF SAID SENSITIVE MATERIAL, SAID BIS-PYRAZOLONE DYE HAVING A METHINE CHAIN CONNECTING TWO PYRAZOLONE NUCLEI THEREOF, SAID METHINE CHAIN CONSISTING OF 5 UNSUBSTITUTED METHINE GROUPS.
 2. A direct-positive light-sensitive material according to claim 1, wherein said bis-pyrazolone dye is selected from the following compounds: 